Production of liquid fuel



' I J6; www sans 22 aufs y Patented Feb. .6, 1945 l u f rltolmcrrou oF LIQUID FUEL Friedrich Martin, oberhausen, and Heinrich Tramm, Oberhausen-Holten, Germany; vested in the Alien Property Custodian Germany January 28, 1935 Appueaun January 22, 19316, serial No. 60,192'

Our invention relates to the productionv of particular advantage bituminous constituents-ofr productsflt for use as liquid fuel for internal combustion engines and for similar purposes. It has particular reference to a processv whereby mixtures of'hydrocarbons can 'be converted into 5 readily volatile, low boiling and inflammable hydrocarbons of the gasoline type.

As is well known to those skilled in the art, in order to produce liquid fuel for internal combustion engines, mixtures of hydrocarbons poor in hydrogen with other hydrocarbons rich inhydrogen have been heat-treated with the result that hydrocarbons of lower boiling point were obtained. Y

One has also reacted carbon monoxide with hydrogen, the product being a mixture of hydrocarbons rich n' hydrogen, which; being little' knocking-proof, are not particularly suitable for use as liquid 'fuel without'having previously un'- dergone a further chemicalltreatment.

' Ithas therefore been tried to subject these products rich in hydrogen, or fractions of same, to a heat treatment wherein a fuel is obtained.

with an octane value, (see the article by A. L.

Forster in NationalPetroleum News 23 (194.1) No. 24, p. not exceeding 63, the knockingproofness of which is not satisfactory at all.

On the other hand this treatment causes considerable quantities of free hydrogen as wel1 as hydrogen combined under the form of gaseous -3 hydrocarbons. such as methane, ethane, ethylene v etc. to bel split off, which are thus lost for the production of liquid fuel.

We have now found that it is possible to produce liquid fuel. having 'a satisfactory octane 35 fragments, magnesia, alumina and the like.

We have further found thatfthe products ob' value if the mixtures of hydrocarbonsresulting g in the reaction of carbonv oxides (CO or'Qn) with hydrogen, .or fractions of'such mixtures which are particularly rich in hydrogen, are submineral coal or brown-coal, which are very poor in hydrogen and are freed, partly or altogether from the ashes, for instance by extracting the bituminous substances or by subjecting same to a slight hydrogenation treatment, wherein the bituminous substances are liqueed at thetemperatures of reaction `and are thereafter T separated from the ashy constituents.

Such a bituminousproduct free from ashes may for instance contain 0.1%v ashes and 39.10% lvolatile constituents, its'upper heatingv value being 8897 heat units/kg., its softening temperature about 231 le. f Y

Here also operation atza pressure above nor' malhas been found preferable.,

If, in order to prepare another .kind of car-` bonaceous material p oor in hydrogen, such as brown-coal, mineral coal, coal emulsions, tars and the like for use -as a starting material in our\ procesa the material is subjected to hydrogen- 7ation with hydrogen gas, the hydrogenation is preferably carried through in a two-stage process. I n the flrststage the highly viscous or liquidstarting products are treated Y'at' temperatures of about 400 C. or above with hydrogen under high pressure ranging for instance vbetween 100 and 300 atmospheres, in the presence of catalysts insensitive to the action of sulfur,

such as compounds of molybdenum, tungsten and metalsiof the fourth, fth and sixth groups of the periodic system, more especially the oxides, sulfides, carbonyls, phosphates and sulfates of these metals, which may be distributed on *carriers such as silica gel, active carbon, pottery tained in the iir'st stage 4of the hydrogenation process .can be reacted advantageously with the jectedtogether with mixtures of hydrocarbons hydrocarbons vobtained when reacting carbony poor in hydrogen to a suitable heat treatment.

. -We have found that the considerable losses in hydrogen and gaseous hydrocarbons encountered, when merely heat-treating the reaction monoxide or carbon dioxide with hydrogen, for thev production of'valuable knocking-proof liquid fuels. f I 1 lIn practising our process, we subject the heavy products from the carbon oxide conversion proc- 5 oils resulting in the first4 hydrogenation stage,

which are rich in hydrogen, are greatly rey duced in our process, so that afar greater yield of liquid fuel, calculated onfthe whole of theL hydrocarbons subjected Jto reaction, is obtained,

this fuel possessing alsb a considerably higher knocking-proofnes's. l

As mixtures of hydrocarbonspoor in hydrogen,

we may use bituminous substances such as tars, mineral oils poor in hydrogen, emulsions of mineral or brown-coal, pitch-coal etc., and with substances hereinbefore mentioned.

All the. reactions occurring inthe process according to this invention are preferablycarried u through inthe presence of hydrogenation cata- 'assenso l an octane value of 63. The benzine gases and vapors lare passed through pipe 2l linto a condenser 2I, from which the non-condensed gases escape at 22, while the condensed liquid hydro- Y carbons are tapped at 2l. The fractions boiling above 200 C. are returned through pipe 24 lnto The process of producing knocking-proof. liquid fuel which comprises mixing hydrocarbons rich in hydrogen, produced by hydrogenating an @x-4 ide of carbonv under substantially normal pres- V sure, with a smaller quantity of a coal extract` which is substantially free from ashesand materially less rich in hydrogen than said hydrocarbons, and subjecting the mixture at a temperature ranging between 300 and '700 C. to a heatl treatment under a pressure not substantially be.

low 60 atmospheres.

FRIEDRICH MARTIN. HEINRICH TRAMM. 

